Synthesis and hydrogen storage properties of Mg-based alloys

Mg-based alloys have been made by mechanical alloying Mg with some transition and non-transition elements. The thermal stability and hydrogen storage properties have been investigated. It was found that mechanical alloying results in a supersaturated solid solution of some elements in the Mg phase. Thermal annealing and/or hydrogenation cause irreversible decomposition of supersaturated solid solution leading to a composite of Mg or MgH₂ with other phase(s) depending on the composition and contents. Therefore, the plateau pressure or thermodynamic properties of hydrogen absorption/desorption of the supersaturated solid solution are no different from that of the Mg composite. While in some equilibrium systems, the formation of Mg solid solution is reversible upon hydrogenation/dehydrogenation. The plateau pressure of the hydrogenation/dehydrogenation is increased due to the interaction of the alloying elements with the Mg lattice in the solid solution. The Mg–Li system is an exception because of the formation of stable LiH upon hydrogenation of Mg(Li) solid solution. No interaction takes place between Mg or MgH₂ with LiH, therefore, no destabilization of MgH₂ is observed.     

Nb、Ta等元素对Zr基大块非晶非晶形成能力及耐腐蚀性影响机理研究

  用计算机编程构造了Zr基非晶合金包含二十面体原子团簇的Zr₂Ni晶体相.用Zr₂Ni晶体相中以Ni原子为中心的二十面体原子团簇模拟Zr基非晶中二十面体团簇.应用实空间的递归方法计算了合金元素取代二十面体原子团簇中心和顶角位置原子时的局域态密度、二十面体原子团簇中中心Ni原子与其近邻合金元素Nb、Ta、Ti、V的总键级积分及团簇的费米能级.结果表明,Nb、Ta、Ti和V取代Zr原子后使其与Ni的键级积分有所降低,使合金的非晶形成能力下降,但Nb、Ta对合金的非晶形成能力影响不大;Nb、V取代Zr使费米能级升高,可使Zr基非晶容易钝化,提高耐蚀性;Ta对Zr基非晶的耐蚀性影响不大.而Ti使Zr基非晶的钝化能力下降.综合合金元素对非晶形成能力和耐腐蚀性的影响,Nb是最有益的合金元素,即在Zr基非晶中,通过加入少量的Nb元素,可以制备出具有较高耐腐蚀性的大块非晶.     

Local atomic structure of Zr–Cu and Zr–Cu–Al amorphous alloys investigated by EXAFS method

We report on extended X-ray absorption fine structure (EXAFS) study of rapidly quenched Zr–Cu and Zr–Cu–Al glassy alloys. The local atomic order around Zr and Cu atoms was investigated. From the EXAFS data fitting the values of coordination number, interatomic distances and mean square atomic displacement were obtained for wide range of compositions. It was found that icosahedral symmetry rather than that of corresponding crystalline analogs dominates in the local atomic structure of Zr–Cu and Zr–Cu–Al amorphous alloys. Judging from bonding preferences we conclude that addition of Al as an alloying element results in considerable deviation from random mixing behavior observed in binary Zr–Cu alloys.     

Thermodynamic Study of Liquid,Crystalline and Quasi-Crystalline Al-Mn Phases

Thermodynamic properties of liquid, intermetallic, and quasi-crystalline phases of the Al-Mn system have been studied using two experimental techniques: integral effusion method and Knudsen-cell mass spectrometry. The functions of the liquid phase followed the laws of associated solution and indicated that three type complexes, AlMn, Al₂Mn, and Al₅Mn, existed in the melt. Phase equilibria calculated using this model and the intermetallic compounds thermodynamic characteristics were in close agreement with phase diagram. The decagonal phase was found to be more stable than the icosahedral quasi-crystals. The calculated enthalpies of the quasi-crystalline phase transformation to the equilibrium crystals were close to the available literature information. The difference between the Gibbs energies of both type quasi-crystals and equilibrium crystalline compositions increases with decreasing temperature. This evidence favors the conclusion that the stabilization of quasi-crystals is entropic in nature and that the quasi-crystalline state, similar to the glassy state in metallic alloys, is only intermediate between liquid and crystals. The conditions of the quasi-crystals formation were found to be closely related to a certain type of the chemical short-range order in liquid, namely to significant mole fraction of the Al₅Mn associative complexes.     

Electrochemical characteristics of Mg2−xZrxNi (x = 0–0.6) electrode alloys prepared by mechanical alloying

The electrode alloys Mg_2−xZr_xNi (x = 0, 0.15, 0.3, 0.45 and 0.6) were prepared by mechanical alloying (MA). Mg in the alloy was partially substituted with Zr in order to improve the electrochemical characteristics of the Mg₂Ni-type alloy. The microstructures and the electrochemical characteristics of the experimental alloys were measured systemically. The effects of substituting Mg with Zr and MA technique on the microstructures and electrochemical performances of the alloys were investigated in detail. The results obtained by XRD, SEM and TEM show that the substitution of Zr is favourable for the formation of an amorphous phase. For a fixed milling time, the amorphous phase in the alloy grows with increasing Zr content. The electrochemical measurement indicates that the substitution of Zr can dramatically enhance the discharge capacity with preferable cycle stability, and it markedly improves the discharge voltage characteristic of the alloys. For x ≤ 0.3, the discharge capacity of the alloys monotonically increases with milling time. But for x > 0.3, it has a maximum value with the change of milling time.     

The correlation of microstructural development and thermal stability of mechanically alloyed multicomponent Fe-Co-Ni-Zr-B alloys

The microstructural evolution of multicomponent Fe_70-x-yCo_xNi_yZr₁₀B₂₀ (x = 0, 7, 21; y = 7, 14, 21, 28) alloys during mechanical alloying (MA) has been studied using XRD, SEM and TEM. Mixtures of elemental and pre-alloyed powders have been transformed initially into the single supersaturated bcc α-Fe solid solution phase for the alloys investigated. Subsequently, an amorphous phase has been obtained in Co-free alloys and Co-containing alloys with high Ni/Co ratios of 1 and 3. However, no amorphous phase was detected in another Co-containing alloy with a lower Ni/Co ratio (e.g. 0.33). The thermal stability of the as-milled powders has been investigated by a combination of DSC and the Pendulum magnetometer experiments. The DSC studies provide information on the thermodynamics and kinetics of crystallization of amorphous structure as a function of alloying contents. The Pendulum magnetometer studies reveal the phase transformation from nanocrystalline bcc α-Fe solid solution to amorphous structure during MA and the thermomagnetization behavior of the as-milled powder.     

合金元素对Zr基大块非晶晶化行为的影响

利用准晶的共轭结构模型构造出了Zr基非晶合金中准晶相的原子结构模型,用递归方法研究了合金元素对非晶晶化过程的影响.结果表明:Zr基非晶合金析出的准晶相存在Zr6Ni,Ni6Zr2种结构,Ni6Zr结构优先析出;合金元素Ag,Pd,Pt,Au固溶于准晶中时,占据Cu,Ni原子的位置,增大近邻原子间的相互作用,这从电子理论角度解释了合金元素Ag,Pd,Pt,Au稳定地促进二十面体准晶(I)相析出的事实.     

Pressure-composition-isotherm behavior of nano-/amorphous Mg<Subscript>2</Subscript>NiH<Subscript>x</Subscript>

It has recently been shown that the hydriding properties of the nanocrystalline metal hydrides are far superior to those of the polycrystalline ones. Especially in the case of the Mg-based hydrogen storage alloys, nanostructural modifications have been studied for the purpose of improving their hydrogenation kinetics. In previous studies, I reported on the successful fabrication of Mg₂NiH_x from Mg and Ni chips with hydrogen induced mechanical alloying (HIMA). Observation of the microstructure showed that the synthesized particles (processed with a 66:1 ball to chips mass ratio and 96 hr HIMA) are composed of amorphous and nanocrystalline composite phases with a grain size of less than 10 nm. The aim of the present work was to examine the hydriding/dehydriding behavior of nanocrystalline metal hydrides using a Sieverts type automatic pressure-composition-isotherm (PCI) apparatus at 393, 423, 453, 483, 513 and 543 K. The specimen was characterized by X-ray diffraction after PCI measurement. The influence of hydrogenation behavior on the phase transition of nano-/amorphous Mg₂Ni is a key factor in commercial application. The particles synthesized at 66:1 BCR and 96 hr HIMA revealed a good hydrogen capacity of 2.25 mass% at 483 K.     

含Ni量对机械合金化Mg—Ni系二元贮氢合金结构和电化学？…

采用机械合金化（ＭＡ）方法制备了ＭｇＮｉｘ（ｘ＝０．５,１．０,１．２５,１．５,２．０）二元贮氢合金。并详细研究了含Ｎｉ量对ＭＡＭｇ－Ｎｉ系二元合金结构和电化学性能的影响。结果表明,当ｘ＝０．５时,ＭＡＭｇＮｉ０．５仍为晶态合金。 形成非晶态结构,且放电容量很低;当ｘ＝１．０～２．０时,ＭＡ Ｍｇ－Ｎｉ二元合金可形成非晶相,且非昌Ｍｇ－Ｎｉ二 合金具有较高的室温放电容量。, 时,在非 组成范围内     

机械合金化非晶Ni50Pd40Si10的形成及加氢催化活性

用机械合金化方法制备了非晶Ni-Pd-Si研究了非晶与晶态Ni-Pd-Si经HF溶液处理后的表面状态及加氢催化活性结果表明:非晶Ni-Pd-Si加氢催化活性比相应的晶态高约2倍     

Rapid solidification and mechanical alloying of Al–Co–Ag ternary alloys for skeletal silver cobalt synthesis

Various precursors of Al₇₅Co_xCu_20−x (x=0–7.5) ternary alloys for formation of the skeletal and metastable materials with large specific surface area were prepared by slow, rapid solidification or mechanical alloying. Their structures were examined by SEM observation, EPMA, X-ray diffraction and DSC measurements. The as-prepared structures of these alloys strongly depended on the applied processes. Three equilibrium phases of AlAg₂, Al₉Co₂ and Al were formed by slow solidification. The formation of the AlAg₂ and Al₉Co₂ phases was suppressed and the super-saturated Al monophase was obtained by rapid solidification in a wide composition range. In the case of mechanical alloying, cobalt atoms were fully dissolved in the Al phase but the formation of the AlAg₂ phase was not suppressed. It was interpreted that the precipitation of the Ag₂Al phase from the super-saturated Al phase was enhanced by plastic strain introduced during mechanical alloying. In mechanical alloying of the Al based alloys including silver, it was difficult to dissolve silver atoms into the Al phase beyond the equilibrium solubility. Rapid solidification proved to be an excellent process to prepare the precursor for chemical leaching.     

球磨时间对Mg2-xZrxNi(x=0～0.6)电极合金微观结构及电化学性能的影响

在不同的球磨时间下,应用机械合金化法制备出Mg2-xZrxNi(x=0,0.15,0.3,0.45,0.6)电极合金.系统地测试了合金的微观结构及电化学性能,研究了球磨时间对合金微观结构及电化学性能的影响.XRD及 TEM的分析结果表明,合金中的非晶相随球磨时间的延长而增加.电化学测试的结果显示,随球磨时间的增加,合金的循环稳定性及放电电压特性得到显著改善.球磨时间对合金容量的影响与合金的成分相关,对于x≤0.3的合金,其放电容量随球磨时间的延长而单调增加;而对于x>0.3的合金,放电容量随球磨时间的增加有一个极大值.     

Crystallographic and electrochemical characteristics of melt-spun Ti-Zr-Ni-Cu alloys

Ti44Zr32Ni22Cu2 and Ti41Zr29Ni28Cu2 alloys were prepared by the melt-spinning method. The phase structure was analyzed by X-ray diffraction,and the electrochemical performances of the melt-spun alloys were investigated. The results indicated that the Ti44Zr32Ni22Cu2 alloy was composed of the icosahedral quasicrystals and amorphous phases,and the Ti41Zr29Ni28Cu2 alloy comprised icosahedral quasicrystals,amorphous,and Laves phases. The maximum discharge capacity was 141 mAh/g for the Ti44Zr32Ni22Cu2 alloy and 181 mAh/g for the Ti41Zr29Ni28Cu2 alloy,respectively. The Ti41Zr29Ni28Cu2 alloy also showed a better high-rate dischargeability and cycling stability. The better electrochemical properties should be ascribed to the high content of Ni,which was beneficial to the electrochemical kinetic properties and made the alloy more resistant to oxidation,as well as to the Laves phase in the Ti41Zr29Ni28Cu2 alloy,which could work as the electro-catalyst and the micro-current collector.     

Preparation of W–Al–Mo ternary alloys by mechanical alloying

Single phase W_XAl₅₀Mo_50−X (X = 40, 30, 20 and 10) powders have been synthesized directly by mechanical alloying (MA). The structural evolutions during MA and subsequent as-milled powders by annealing at 1400 °C have been analyzed using X-ray diffraction (XRD). Different from the Mo₅₀Al₅₀ alloy, W₄₀Al₅₀Mo₁₀ and W₃₀Al₅₀Mo₂₀ alloys were stable at 1400 °C under vacuum. The results of high-pressure sintering indicated that the microhardnesses of two compositions, namely W₄₀Al₅₀Mo₁₀ and W₃₀Al₅₀Mo₂₀ alloys have higher values compared with W₅₀Al₅₀ alloy.     

Structural and hyperfine properties of Ti48Zr7Fe18 nano-compounds and its hydrides

It is well established that Ti-based nano-alloys are able to absorb hydrogen with relatively high hydrogen to metal ratio of 4/3. In this study the Ti₄₈Zr₇Fe₁₈ nano-compound, prepared by mechanical alloying (MA), has been investigated. In its initial state the compound is amorphous, however upon thermal treatment it transforms to the quasicrystalline icosahedral structure (i-phase), which is based on the Mackay cluster type. Structural characterization of the sample was made by means of XRD measurements. Thermodynamic properties were studied by differential scanning calorimetry (DSC) and thermal desorption spectroscopy (TDS). To find the influence of hydrogen and structure type on hyperfine interactions the Mössbauer spectroscopy (MS) experiment was performed, as well. The amorphous sample after MA was hydrogenated in order to unveil hydrogen influence on crystal properties of the sample. Upon hydrogenation of the amorphous sample a decomposition into simple hydrides took place.     

Microstructural, thermal and magnetic properties of amorphous/nanocrystalline FeCrMnN alloys prepared by mechanical alloying and subsequent heat treatment

Amorphous FeCrMnN alloys were synthesized by mechanical alloying (MA) of the elemental powder mixtures under a nitrogen gas atmosphere. The phase identification and structural properties, morphological evolution, thermal behavior and magnetic properties of the mechanically alloyed powders were evaluated by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and vibrating sample magnetometer (VSM), respectively. According to the results, at the low milling times the structure consists of the nanocrystalline ferrite and austenite phases. By progression of the MA process, the quantity and homogeneity of the amorphous phase increase. At sufficiently high milling times (>120 h), the XRD pattern becomes halo, indicating complete amorphization. The results also show that the amorphous powders exhibit a wide supercooled liquid region. The crystallization of the amorphous phase occurs during the heating cycle in the DSC equipment and the amorphous phase is transformed into the crystalline compounds containing ferrite, CrN and Cr₂N. The magnetic studies reveal that the magnetic coercivity increases and then decreases. Also, the saturation magnetization decreases with the milling time and after the completion of the amorphization process (>120 h), the material shows a paramagnetic behavior. Although the magnetic behavior does not considerably change by heating the amorphous powders up to the crystallization temperature via DSC equipment, the material depicts a considerable saturation magnetization after the transformation of the amorphous phase to the nanocrystalline compounds.     

First-Principle Calculations of the MgYA_4(A=Co and Ni)Phase with AuBe_5-Type Structure

First-principles calculations have been performed to study the structural,mechanical and magnetic properties of the MgYCo_4 and MgYNi_4 phases in AuBe_5-type structure.The obtained values of cohesive energy as well as formation energy prove that the MgYCo_4 and MgYNi_4 phases have a good combination of structural stability and alloying ability,which is also supported by electronic structure.It is found that the magnetic moment of the MgYCo_4 phase is 19.06 μ_B per unit cell mainly owed to the 3d state of Co atom,and the MgYNi_4 phase exhibits no magnetism.Both the trigonal shear constant C_(44) and the shear modulus G of the Mg YNi_4 phase are larger than those of the MgYCo_4 phase.Plasticity of alloys has been estimated by the C_(11)-C_(12) and Young's modulus E,and C_(12)-C_(44),shear to bulk modulus ratio G/B and Poisson's ratio v have been studied to predict the ductility of alloys.According to the calculated results,the MgYCo_4 phase has better plasticity as well as ductility,compared with the MgYNi_4 phase.     

MgNi非晶合金的制备及电极性能的研究

用机械合金化的方法研究了MgNi非晶相的形成效率、合成物相组成和相结构的演变以及电极性能与机械球磨工艺的依赖关系。模拟电池法测量Mg-Ni合成物的电极性能,发现放电容量的大小与非晶相的形成效率成正比,球磨50～60h的MgNi非晶具有最大的放电容量,继续延长球磨时间导致放电容量下降。基于MgNi非晶相形成过程的相组成和相结构,探讨了合成物电极性能的变化规律。     

An Iron-Based High-Entropy Alloy with Highly Efficient Degradation for p-Nitrophenol

High-entropy alloys(HEAs) have attracted widespread attention due to their excellent mechanical properties. However, their functional properties arising from the supersaturated solid solution state can be improved. Advanced oxidation processes(AOPs) are considered to be an effective method for decomposing organic pollutants, and HEAs are proposed as effective candidates for AOP catalysts. Currently, several HEAs used for organic pollutant degradation are prepared through mechanical alloying. In ...     

Effect of Sn on synthesis of nanocrystalline Ti-based alloy with fcc structure

The effect of the amount of Sn on the formation of fcc phase in Ti−13Ta−xSn (x=3, 6, 9 and 12, at.%) alloys was studied. The alloys were synthesized by mechanical alloying using a planetary mill, jar and balls of stabilized yttrium. Using Rietveld refinement, it was found that the obtained fcc phase has crystallite size smaller than 10 nm and microstrain larger than 10⁻³. Both conditions are required to form an fcc phase in Ti-based alloys. For all samples, the microstructure of the fcc phase consists of equiaxial crystallites with sizes smaller than 10 nm. The largest presence of fcc phase in the studied Ti alloy was found with 6 at.% Sn, because this alloy exhibits the largest microstrain (1.5×10⁻²) and crystallite size of 6.5 nm. Experimental data reveal that a solid solution and an amorphous phase were formed during milling. The necessary conditions to promote the formation of solid solution and amorphous phases were determined using thermodynamic calculations. When the amount of Sn increases, the energy required to form an amorphous phase varies from approximately 10 to approximately −5 kJ/mol for 3 and 12 at.% Sn, respectively. The thermodynamic calculations are in agreement with XRD patterns analysis and HRTEM results.